EP2576749B1 - Dishwasher products in a compacted form - Google Patents

Description

The present application describes automatic dishwashing detergents which are in the form of shaped bodies and also automatic dishwashing processes using these shaped bodies and the use of these shaped bodies for removing soiling in automatic dishwashing.

Dishwashing detergents are available to consumers in a variety of forms. In addition to the traditional liquid hand dishwashing detergents, with the spread of household dishwashers, automatic dishwashing detergents in particular have gained great importance. These automatic dishwashing detergents are typically offered to the consumer in solid form, for example as a powder or as tablets, but increasingly also in liquid form.

One of the main goals of the manufacturers of machine cleaning agents is to improve the cleaning and rinsing performance of these agents, with more recent attention being paid to the cleaning and rinsing performance in low-temperature cleaning cycles or in cleaning cycles with reduced water consumption.

This application was based on the object of providing an automatic dishwasher detergent with improved cleaning properties, these improved cleaning properties in particular also in low-temperature cleaning processes, in particular in cleaning processes with washing liquor temperatures of 50 ° C. or below, and / or in short-lasting cleaning processes, in particular in cleaning processes a duration of less than 60 minutes should be achieved. The improved cleaning properties should be achieved in particular with regard to bleachable soiling, in particular tea soiling.

Automatic dishwashing detergents which contain cobalt-based bleach catalysts and cross-linked polyvinylpyrrolidone are disclosed in the laid-open specification US 2002/0160930 A1 disclosed.

Bleach-enhancing transition metal salts or transition metal complexes as bleach catalysts are described in the laid-open specification DE 10 2007 059 968 A1 disclosed.

This object was achieved by a molded body which contains polyvinylpyrrolidone particles and at least one bleach catalyst.

A first subject of the present invention is therefore dishwashing detergents in the form of a

Shaped body, especially a compact, especially a tablet, characterized in that it contains polyvinylpyrrolidone particles and at least one bleach catalyst. The polyvinylpyrrolidone particles (PVP particles) have an average particle diameter of 100 to 150 μm and preferably consist of cross-linked polyvinylpyrrolidone. A manganese complex with the macromolecular ligands 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), 1,4,7-triazacyclononane (TACN) and / or 2-methyl-1,4 is used as the bleaching catalyst , 7-trimethyl-1,4,7-triazacyclononane (Me / Me-TACN), selected from [Mn ^III ₂ (µ-O) ₁ (µ-OAc) ₂ (TACN) ₂ ] (ClO ₄ ) ₂ , [ Mn ^III Mn ^IV (µ-O) ₂ (µ-OAc) ₁ (TACN) ₂ ] (BPh ₄ ) ₂ , [Mn ^IV 4 (µ-O) ₆ (TACN) ₄ ] (ClO ₄ ) ₄ , [Mn ^III ₂ (µ-O) ₁ (µ-OAc) ₂ (Me-TACN) ₂ ] (ClO ₄ ) ₂ , [Mn ^III Mn ^IV (µ-O) ₁ (µ-OAc) ₂ (Me-TACN) ₂ ] (ClO ₄ ) ₃ , [Mn ^IV ₂ (µ-O) ₃ (Me-TACN) ₂ ] (PF ₆ ) ₂ and [Mn ^IV ₂ (µ-O) ₃ (Me / Me-TACN) ₂ ] ( PF ₆ ) ₂ , inserted.

The present invention also relates to an automatic dishwashing process using the aforementioned shaped bodies. The dishwashing process is preferably carried out at a liquor temperature below 60.degree. C., preferably below 50.degree. In a preferred embodiment, the dishwashing process takes a maximum of 90 minutes, in particular a maximum of 75 minutes, particularly preferably a maximum of 60 minutes. In particular embodiments, the dishwashing process takes a maximum of 50, 40 or 30 minutes.

The present invention also relates to the use of a dishwashing agent according to the invention for removing, in particular improved removal, of bleachable stains, in particular tea stains.

The subject of the present application is automatic dishwashing detergents. In accordance with this application, automatic dishwashing agents are compositions which can be used to clean soiled dishes in an automatic dishwashing process. The automatic dishwashing agents according to the invention thus differ, for example, from the automatic rinse aid agents, which are always used in combination with automatic dishwashing agents and do not develop their own cleaning effect.

The automatic dishwashing detergents according to the invention are in the form of a shaped body, preferably a compact, especially a tablet. However, they can also be present in combination with other supply forms, in particular in combination with solid supply forms such as powder, granules or extrudates or in combination with liquid supply forms based on water and / or organic solvents.

Agents according to the invention can be packaged as single-phase or multi-phase products. Automatic dishwashing detergents with one, two, three or four phases are particularly preferred. Automatic dishwashing detergents, characterized in that they are in the form of a prefabricated dosage unit with two or more phases, are particularly preferred. Especially Two-phase or multiphase tablets are particularly preferred, for example two-layer tablets, in particular two-layer tablets with a recess and a shaped body located in the recess.

Automatic dishwashing detergents according to the invention are preferably pre-packaged into metering units. These metering units preferably include the amount of washing or cleaning-active substances necessary for a cleaning cycle. Preferred dosing units have a weight between 12 and 30 g, preferably between 14 and 26 g and in particular between 15 and 22 g.

The volume of the aforementioned metering units and their spatial shape are particularly preferably selected so that the pre-assembled units can be metered via the metering chamber of a dishwasher. The volume of the dosing unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml and in particular between 15 and 25 ml.

The automatic dishwashing detergents according to the invention, in particular the prefabricated dosage units, particularly preferably have a water-soluble coating.

Moldings according to the invention contain polyvinylpyrrolidone particles. Among other things, these particles facilitate the disintegration of the shaped body and serve as disintegration aids or tablet disintegrants. In addition, however, it has been found that the combination of the polyvinylpyrrolidone particles with anionic polymers also improves the cleaning performance of cleaning agents according to the invention. The function of the PVP particles is therefore not limited solely to facilitating the disintegration of the moldings.

According to the invention, it has been found to be particularly advantageous to use polyvinylpyrrolidone particles with an average particle diameter of 100 to 150 μm, in particular with an average particle diameter of 110 to 130 μm.

In the context of the present invention, the term “mean particle diameter” or “mean diameter” is to be understood as meaning the volume-mean D ₅₀ particle diameter, which can be determined by conventional methods. The volume-average D ₅₀ particle diameter is that point in the particle size distribution at which 50% by volume of the particles have a smaller diameter and 50% by volume of the particles have a larger diameter. The mean particle diameter can in particular be determined with the aid of dynamic light scattering, which is usually carried out on dilute suspensions containing, for example, 0.01 to 1% by weight of capsules.

According to the invention, the PVP particles not only have an average particle diameter of 100 to 150 μm, in particular 110 to 130 μm, but, moreover, the particle size of the particles used is preferably completely within the specified intervals. This is ensured by using grain size fractions with the specified particle sizes, which were obtained by a sieving process.

The moldings according to the invention, in particular the detergent tablets, are preferably produced in a manner known to the person skilled in the art, by pressing particulate starting substances. To produce the tablets, the premix is compressed in a so-called die between two punches to form a solid compact. This process, which is referred to as tabletting for short in the following, is divided into four sections: dosing, compression (elastic deformation), plastic deformation and ejection. Tableting is preferably carried out on what are known as rotary presses.

• Verwendung von Kunststoffeinlagen mit geringen Dickentoleranzen
• Geringe Umdrehungszahl des Rotors
• Große Füllschuhe
• Abstimmung des Füllschuhflügeldrehzahl auf die Drehzahl des Rotors
• Füllschuh mit konstanter Pulverhöhe
• Entkopplung von Füllschuh und Pulvervorlage

In the case of tableting with rotary presses, it has proven advantageous to carry out the tableting with the lowest possible fluctuations in the weight of the tablet. In this way, the fluctuations in hardness of the tablet can also be reduced. The minimization of weight fluctuations can be achieved in the following ways:

• Use of plastic inserts with small thickness tolerances
• Low speed of the rotor
• Big filling shoes
• Adjustment of the filling shoe wing speed to the speed of the rotor
• Filling shoe with constant powder height
• Decoupling of the filling shoe and powder feed

The ingredients intended for tabletting can be filled into the die in the form of a common particulate premix at the same time or in the form of individual, separate powders or granules or at the same time, the dosage of a pre-prepared particulate premix being preferred.

According to the invention, it was surprisingly found that granulates used according to the invention for producing the shaped bodies can be compressed particularly well. Thus, preferably using a pressing force of 40 to 65 kN, particularly preferably 48 to 60 kN, compacts with a hardness in the range from 150 to 250 N, in particular in the range from 200 to 230 N, which are also particularly good Have flow behavior. The granules can thus preferably be pressed with a relatively low pressing force to give compacts with a relatively high hardness, which moreover preferably have very good flow behavior. Conversely, it is correspondingly advantageous that for the production of compact data lower hardness, a lower pressing force has to be used than for the production of conventional compacts.

Another object particularly preferred according to the invention therefore also represents a shaped body, in particular a compact, especially a cleaning tablet, which is a mixture of polyvinylpyrrolidone particles with an average particle diameter of 100 to 150 μm, in particular 110 to 130 μm, and at least one anionic copolymer selected from copolymeric polycarboxylic acids and copolymeric polysulfonic acids and preferably has very good flow behavior.

The PVP particles are preferably present in compositions according to the invention in an amount of 0.1 to 5% by weight, in particular in an amount of 0.2 to 3% by weight, especially in an amount of 0.3 to 1, 8% by weight

The effect of disintegrants is usually that they increase their volume when water gets in, whereby on the one hand the intrinsic volume increases (swelling), but on the other hand a pressure can be generated through the release of gases, which causes the tablet to disintegrate into smaller particles . In addition to the PVP particles, further disintegrants can also be contained in molded bodies according to the invention, for example carbonate / citric acid systems or carbonate in combination with other organic acids, synthetic polymers or natural polymers or modified natural substances such as cellulose and starch and their derivatives as well as alginates or Casein derivatives can be used as further disintegrants. Furthermore, gas-generating shower systems can also be used as further disintegrants. Preferred effervescent systems consist of at least two components that react with one another to form gas, for example alkali metal carbonate and / or hydrogen carbonate and an acidifying agent which is suitable for releasing carbon dioxide from the alkali metal salts in aqueous solution. An acidifying agent which releases carbon dioxide from the alkali salts in aqueous solution is, for example, citric acid.

The further disintegration aids, if used, are preferably used in amounts of 0.1 to 10% by weight, preferably 0.2 to 5% by weight and in particular 0.5 to 2% by weight, each based on the total weight of the disintegration aid containing agent used.

In a preferred embodiment, the shaped body according to the invention contains no further disintegration aids apart from the PVP particles.

Automatic dishwashing detergents according to the invention contain at least one bleach catalyst as a further component. These substances are bleach-intensifying transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru - or Mo-salen complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.

Manganese complexes in the II, III, IV or V oxidation state, which preferably contain one or more macrocyclic ligand (s) with the donor functions N, NR, PR, O and / or S, are used with particular preference. According to the invention, ligands are used which have nitrogen donor functions. It is particularly preferred to use bleach catalyst (s) in the agents according to the invention which have 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), 1,4,7-triazacyclononane (TACN ), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane (Me / Me-TACN) and / or 2-methyl-1,4,7-triazacyclononane (Me / TACN). According to the invention, a manganese complex with the macromolecular ligands 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), 1,4,7-triazacyclononane (TACN) and / or 2-methyl-1, is used as the bleach catalyst. 4,7-trimethyl-1,4,7-triazacyclononane (Me / Me-TACN), selected from [Mn ^III ₂ (µ-O) ₁ (µ-OAc) ₂ (TACN) ₂ ] (ClO4) ₂ , [ Mn ^III Mn ^IV (µ-O) ₂ (µ-OAc) ₁ (TACN) ₂ ] (BPh ₄ ) ₂ , [Mn ^IV ₄ (µ-O) ₆ (TACN) ₄ ] (ClO ₄ ) ₄ , [Mn ^III ₂ (µ-O) ₁ (µ-OAc) ₂ (Me-TACN) ₂ ] (ClO ₄ ) ₂ , [Mn ^III Mn ^IV (µ-O) ₁ (µ-OAc) ₂ (Me-TACN) ₂ ] (ClO ₄ ) ₃ , [Mn ^IV ₂ (µ-O) ₃ (Me-TACN) ₂ ] (PF ₆ ) ₂ and [Mn ^IV ₂ (µ-O) ₃ (Me / Me-TACN) ₂ ] ( PF ₆ ) ₂ (OAc = OC (O) CH ₃ ) is used.

Automatic dishwashing detergents, characterized in that they also contain a bleach catalyst selected from the group of the bleach-enhancing transition metal salts and transition metal complexes, preferably from the group of the complexes of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me ₃ -TACN ) or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me ₄ -TACN) are preferred according to the invention, since the aforementioned bleach catalysts in particular can significantly improve the cleaning result.

The aforementioned bleach-intensifying transition metal complexes, in particular with the central atoms Mn and Co, are used in customary amounts, preferably in an amount up to 5% by weight, in particular from 0.0025% by weight to 1% by weight and particularly preferably from 0, 01% by weight to 0.30% by weight, based in each case on the total weight of the bleach catalyst-containing compositions, are used. In special cases, however, more bleach catalyst can also be used.

The dishwashing detergents according to the invention also preferably contain at least one bleach. Oxygen bleaches are preferred as the bleaching agent. Sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance among the compounds which serve as bleaching agents and produce H ₂ O ₂ in water. Further Usable bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and peracid salts or peracids which provide H ₂ O ₂ , such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid or diperdodecanedioic acid.

Furthermore, bleaches from the group of organic bleaches can also be used. Typical organic bleaching agents are the diacyl peroxides, e.g. Dibenzoyl peroxide. Further typical organic bleaching agents are the peroxy acids, the alkyl peroxy acids and the aryl peroxy acids being mentioned as examples.

Preferred automatic dishwashing agents according to the invention are characterized in that they contain an oxygen bleach, preferably sodium percarbonate, particularly preferably a coated sodium percarbonate. The weight fraction of the bleach, based on the total weight of the detergent or cleaning agent, is preferably Embodiments between 2 and 30% by weight, preferably between 4 and 20% by weight and in particular between 6 and 15% by weight.

The dishwashing detergents according to the invention also preferably contain at least one bleach activator. Under perhydrolysis conditions, these compounds give aliphatic peroxocarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid. Substances which carry O- and / or N-acyl groups with the number of carbon atoms mentioned and / or optionally substituted benzoyl groups are suitable. Multiple acylated alkylenediamines are preferred, tetraacetylethylenediamine (TAED) having proven particularly suitable.

Automatic dishwashing detergents, characterized in that the bleach activator used is a bleach activator from the group of acetylated amines, preferably tetraacetylenediamine (TAED), are preferred according to the invention. These bleach activators, in particular TAED, are preferably used in amounts of up to 10% by weight, in particular 0.1% by weight to 10% by weight, especially 0.5 to 8% by weight and particularly preferably 1.0 to 6% by weight Wt .-%, used.

In a preferred embodiment, dishwashing detergents according to the invention also contain at least one anionic polymer. Preferred anionic polymers here are the copolymeric polycarboxylates and the copolymeric polysulfonates.

The proportion by weight of the anionic polymer in the total weight of the automatic dishwashing agent according to the invention is in a preferred embodiment from 0.1 to 20% by weight, preferably from 0.5 to 18% by weight, particularly preferably from 1.0 to 15% by weight. % and especially from 4 to 14% by weight.

Automatic dishwashing detergents according to the invention, characterized in that the copolymeric anionic polymer is selected from the group of the hydrophobically modified polycarboxylates and polysulfonates, is a particularly preferred subject, since the hydrophobic modification of the anionic copolymers improves the rinsing and drying properties of these agents while simultaneously reducing the formation of deposits can be achieved.

The copolymers can have two, three, four or more different monomer units.

Preferred copolymeric polysulfonates contain, in addition to monomer (s) containing sulfonic acid groups, at least one monomer from the group of unsaturated carboxylic acids.

The unsaturated carboxylic acid (s) used is / are with particular preference unsaturated carboxylic acids of the formula R ¹ (R ² ) C =C (R ³ ) COOH, in which R ¹ to R ³ independently of one another represent -H, -CH ₃ , a straight-chain or branched saturated alkyl radical with 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical with 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted with -NH ₂ , -OH or -COOH as defined above or for -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-phenyte acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof. The unsaturated dicarboxylic acids can of course also be used.

According to the invention, copolymers of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid are particularly preferably used as copolymeric polycarboxylates. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven particularly suitable. Their relative molecular weight, based on free acids, is generally from 2000 to 70,000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.

The monomers containing sulfonic acid groups are those of the formula

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H

preferred, in which R ⁵ to R ⁷ independently of one another represent -H, -CH ₃ , a straight-chain or branched saturated alkyl radical with 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical with 2 to 12 carbon atoms, with - NH ₂ , -OH or -COOH-substituted alkyl or alkenyl radicals or -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optionally present spacer group , which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - , -C (O) -NH-C (CH ₃ ) ₂ -CH ₂ - and -C (O) -NH-CH (CH ₃ ) -CH ₂ -.

Preferred among these monomers are those of the formulas

H ₂ C = CH-X-SO ₃ H

H ₂ C = C (CH ₃ ) -X-SO ₃ H

HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H,

in which R ⁶ and R ⁷ are independently selected from -H, -CH _3, -CH ₂ CH _3, - CH ₂ CH ₂ CH ₃ and -CH (CH _{3) 2} and X is an optionally present spacer group is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ -, - C (O) -NH-C (CH ₃ ) ₂ -CH ₂ - and -C (O) -NH-CH (CH ₃ ) -CH ₂ -.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3- Methacrylamido-2-hydroxy-propanesulphonic acid, allylsulphonic acid, methallylsulphonic acid, allyloxybenzenesulphonic acid, methallyloxybenzenesulphonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulphonic acid, 2-methyl-2-propen1-sulphonic acid, 3-sulphate , Sulfomethacrylamide, sulfomethyl methacrylamide and mixtures of the acids mentioned or their water-soluble salts.

In the polymers, the sulfonic acid groups can be wholly or partly in neutralized form, i.e. that the acidic hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions. The use of partially or fully neutralized copolymers containing sulfonic acid groups is preferred according to the invention.

The monomer distribution of the copolymers preferably used according to the invention is, in the case of copolymers which only contain monomers containing carboxylic acid groups and monomers containing sulphonic acid groups, preferably in each case from 5 to 95% by weight; the proportion of the monomer containing sulphonic acid groups is particularly preferably 50 to 90% by weight. % and the proportion of the carboxylic acid group-containing monomer 10 to 50% by weight, the monomers here are preferably selected from those mentioned above.

The molar mass of the sulfo copolymers preferably used in accordance with the invention can be varied in order to adapt the properties of the polymers to the desired intended use. Preferred automatic dishwashing detergents are characterized in that the copolymers have molar masses from 2000 to 200,000 gmol ^-1 , preferably from 4000 to 25,000 gmol ^-1 and in particular from 5000 to 15,000 gmol ^-1 .

In a further preferred embodiment, the copolymers furthermore comprise at least one nonionic, preferably hydrophobic, monomer in addition to monomer containing carboxyl groups and monomer containing sulfonic acid groups. By using this hydrophobically modified polymers, in particular, it was possible to improve the rinse aid performance of automatic dishwashing agents according to the invention.

1. i) Carbonsäuregruppen-haltige Monomer(e)
2. ii) Sulfonsäuregruppen-haltige Monomer(e)
3. iii) nichtionische Monomer(e)

enthält, werden erfindungsgemäß bevorzugt.Automatic dishwashing agent, characterized in that the automatic dishwashing agent comprises a copolymer as an anionic copolymer

1. i) Carboxylic acid group-containing monomer (s)
2. ii) Monomer (s) containing sulfonic acid groups
3. iii) nonionic monomer (s)

are preferred according to the invention.

The nonionic monomers used are preferably monomers of the general formula R ¹ (R ² ) C =C (R ³ ) -XR ⁴ , in which R ¹ to R ³ independently of one another represent -H, -CH ₃ or -C ₂ H ₅ , X stands for an optionally present spacer group which is selected from -CH ₂ -, -C (O) O- and -C (O) -NH-, and R ^{4 stands} for a straight-chain or branched, saturated alkyl radical having 2 to 22 carbon atoms or represents an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms.

Particularly preferred nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4-trimethylpentene-2, 2,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethylhexene-1, 3,5-dimethylhexene-1, 4 , 4-dimethylhexane-1, ethylcyclohexyn, 1-octene, α-olefins with 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C22-α-olefin, 2-styrene, α -Methylstyrene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, methyl acrylate, ethyl acrylate, propyl acrylate, methyl acrylate, methyl acrylate, butyl acrylate, acrylate - (Methyl) acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, N - (2-ethylhexyl) acrylamide, octyl acrylate, methacr ylsäureoctylester, N - (octyl) acrylamide, lauryl acrylate, lauryl methacrylate, N- (lauryl) acrylamide, stearyl acrylate, stearyl methacrylate, N - (stearyl) acrylamide, behenyl acrylate, Methacrylsäurebehenylester and N - (behenyl) acrylamide or mixtures thereof.

In a preferred embodiment, dishwashing detergents according to the invention also contain at least one nonionic surfactant of the general formula R ¹ O (AlkO) _x M (OAlk) _y OR ² , where R ¹ and R ² independently represent a branched or unbranched, saturated or unsaturated, optionally hydroxylated one Are alkyl radicals having 4 to 22 carbon atoms; Alk represents a branched or unbranched alkyl radical having 2 to 4 carbon atoms; x and y are independently of one another for values between 1 and 70; and
M represents an alkyl radical from the group CH ₂ , CHR ³ , CR ³ R ⁴ , CH ₂ CHR ³ and CHR ³ CHR ⁴ , where R ³ and R ⁴ independently of one another represent a branched or unbranched, saturated or unsaturated alkyl radical with 1 to 18 carbon atoms.

• R, R¹ und R² unabhängig voneinander für einen Alkylrest oder Alkenylrest mit 6 bis 22 Kohlenstoffatomen;
• x und y unabhängig voneinander für Werte zwischen 1 und 40 stehen

In a first preferred embodiment, automatic dishwashing agents according to the invention contain a surfactant of the general formula R ¹ —CH (OH) CH ₂ —O (CH ₂ CH ₂ O) _x CH ₂ CHR (OCH ₂ CH ₂ ) _y O — CH as a nonionic surfactant ₂ CH (OH) -R ² , where

• R, R ¹ and R ² independently of one another represent an alkyl radical or alkenyl radical having 6 to 22 carbon atoms;
• x and y independently represent values between 1 and 40

In particular, compounds of the general formula R ¹ —CH (OH) CH ₂ —O (CH ₂ CH ₂ O) _x CH ₂ CHR (OCH ₂ CH ₂ ) _y O — CH ₂ CH (OH) —R ² , in are preferred where R is a linear, saturated alkyl radical having 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms, and x and y, independently of one another, have values from 20 to 30. Corresponding compounds can be obtained, for example, by reacting alkyl diols HO-CHR-CH ₂ -OH with ethylene oxide, followed by a reaction with an alkyl epoxide to close off the free OH functions with the formation of a dihydroxy ether.

• R¹ und R² unabhängig voneinander für einen Alkylrest oder Alkenylrest mit 4 bis 22 Kohlenstoffatomen;
• R³ und R4 unabhängig voneinander für H oder für einen Alkylrest oder Alkenylrest mit 1 bis 18 Kohlenstoffatomen und
• x und y unabhängig voneinander für Werte zwischen 1 und 40 stehen;

In a further preferred embodiment, automatic dishwashing detergents according to the invention contain a surfactant of the general formula R ¹ -O (CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² as the nonionic surfactant, in which

• R ¹ and R ² independently of one another represent an alkyl radical or alkenyl radical having 4 to 22 carbon atoms;
• R ³ and R 4 independently of one another represent H or an alkyl radical or alkenyl radical having 1 to 18 carbon atoms and
• x and y are independently of one another for values between 1 and 40;

Particularly preferred here are compounds of the general formula R ¹ -O (CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² , in which R ³ and R ^{4 are} H and the indices x and y independently of one another assume values from 1 to 40, preferably from 1 to 15.

Particularly preferred are compounds of the general formula R ¹ -O (CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² , in which the radicals R ¹ and R ² independently of one another are saturated alkyl radicals with 4 to 14 represent carbon atoms and the indices x and y independently assume values from 1 to 15 and in particular from 1 to 12.

Also preferred are those compounds of the general formula R ¹ -O (CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² in which one of the radicals R ¹ and R ^{2 is} branched.

Compounds of the general formula R ¹ -O (CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² , in which the indices x and y independently assume values from 8 to 12, are very particularly preferred.

The weight fraction of the nonionic surfactant of the general formula R ¹ O (AlkO) _x M (OAlk) _y OR ^{2 in} the total weight of the automatic dishwashing agent according to the invention is in a preferred embodiment between 0.05 and 10% by weight, preferably between 0.1 and 8% by weight, preferably between 0.5 and 5% by weight and in particular between 1 and 3% by weight.

Dishwashing detergents according to the invention also preferably contain builder (s) and enzyme (s) to ensure their cleaning effect.

Automatic dishwashing agents according to the invention preferably contain one or more builders as a further constituent. The proportion by weight of the builders in the total weight of automatic dishwashing agents according to the invention is preferably 15 to 80% by weight and in particular 20 to 70% by weight. The builders include in particular carbonates, phosphates, citrates, organic cobuilders and silicates.

The use of carbonate (s) and / or hydrogen carbonate (s), preferably alkali metal carbonate (s), particularly preferably sodium carbonate, in amounts of from 2 to 30% by weight, preferably from 4 to 28% by weight and in particular, is particularly preferred from 8 to 24% by weight, based in each case on the weight of the automatic dishwashing agent.

The use of phosphate is also preferred. Of the large number of commercially available phosphates, the alkali metal phosphates, with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), are of greatest importance in the detergent and cleaning agent industry.

Alkali metal phosphate is the summary name for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which metaphosphoric acids (HPO ₃ ) _n and orthophosphoric acid H ₃ PO ₄ can be distinguished in addition to higher molecular representatives. The phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts or lime incrustations in fabrics and also contribute to cleaning performance.

Phosphates particularly preferred according to the invention are pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (Potassium tripolyphosphate). Sodium potassium tripolyphosphates are also preferably used according to the invention.

If, in the context of the present application, phosphates are used as washing or cleaning-active substances in the automatic dishwashing detergents, they contain quantities of phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate) from 5 to 60% by weight, preferably from 15 to 45% by weight and in particular from 20 to 40% by weight, based in each case on the weight of the automatic dishwasher detergent.

Organic cobuilders that may be mentioned are, in particular, polycarboxylates / polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals, dextrins and organic cobuilders. These substance classes are described below.

Organic builder substances which can be used are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or its sodium salts, polycarboxylic acids being understood as meaning those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, as well as mixtures of these. In addition to their builder effect, the free acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value in washing or cleaning agents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these should be mentioned in particular.

Particularly preferred automatic dishwashing agents according to the invention contain citrate as one of their essential builders. Automatic dishwashing detergents, characterized in that they contain 2 to 40% by weight, preferably 5 to 30% by weight and in particular 7 to 20% by weight citrate, are preferred according to the invention.

Like the phosphates, the citrates are preferably used in combination with carbonates and / or hydrogen carbonate. Preferred automatic dishwashing detergents are therefore characterized by a builder combination of phosphate and carbonate / hydrogen carbonate or of citrate and carbonate / hydrogen carbonate (cf. Tables 1a and 1b below). Naturally, however, builder combinations of phosphate, citrate and carbonate / hydrogen carbonate can also be realized.

Particularly preferred automatic dishwashing agents are characterized in that the dishwashing agent contains at least two builders from the group of phosphates, carbonates and citrates, the weight fraction of these builders, based on its total weight of the automatic dishwashing agent, preferably 5 to 80% by weight, preferably 15 to 75% by weight and in particular 30 to 70% by weight. The combination of two or more builders from the above-mentioned group has proven to be advantageous for the cleaning and rinsing performance of automatic dishwashing agents according to the invention.

Polymeric polycarboxylates are also suitable as builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 2000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates from this group, which have molecular weights from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can be preferred.

The content of (homo) polymeric polycarboxylates in the automatic dishwashing detergents is preferably 0.5 to 20% by weight and in particular 3 to 10% by weight.

Automatic dishwashing agents according to the invention can use crystalline layered silicates of the general formula NaMSi _x O _{2x + 1} · y H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, as a builder particularly preferred values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20.

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ module of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 to 1: 2.6, which are preferably delayed in dissolution and have secondary washing properties.

In preferred automatic dishwashing agents according to the invention, the silicate content, based on the total weight of the automatic dishwashing agent, is limited to amounts below 10% by weight, preferably below 5% by weight and in particular below 2% by weight. Automatic dishwashing agents according to the invention which are particularly preferred are silicate-free.

Further suitable builders which can be used as the only builders, but in particular in combination with citrate, are methylgylcinediacetic acid (MGDA) and glutamic acid-N, N-diacetic acid (GLDA). These builders are preferably used in amounts of 5 to 60 % By weight, in particular 10 to 40% by weight, are used in automatic dishwashing agents according to the invention.

In addition to the aforementioned builders, the agents according to the invention can contain alkali metal hydroxides. These alkali carriers are preferably only used in small amounts in the cleaning agents, preferably in amounts below 10% by weight, preferably below 6% by weight, preferably below 5% by weight, particularly preferably between 0.1 and 5% by weight. and in particular between 0.5 and 5% by weight, based in each case on the total weight of the cleaning agent. Alternative automatic dishwashing detergents are free from alkali metal hydroxides.

Dishwashing detergents according to the invention preferably contain enzyme (s) as a further component. These include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are in principle of natural origin; Based on the natural molecules, improved variants are available for use in detergents or cleaning agents, and these are accordingly preferred. Washing or cleaning agents preferably contain enzymes in total amounts of 1 × 10 ⁻⁶ to 5% by weight, based on active protein. The protein concentration can be determined using known methods, for example the BCA method or the biuret method.

Among the proteases, those of the subtilisin type are preferred. Examples of this are the subtilisins BPN 'and Carlsberg as well as their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the subtilases, but no longer the subtilisins in the narrower sense of the term, thermitase, Proteinase K and the proteases TW3 and TW7.

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae as well as the improved further developments of the aforementioned amylases for use in detergents and cleaning agents. Furthermore, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).

According to the invention, lipases or cutinases can also be used, in particular because of their triglyceride-cleaving activities, but also to generate peracids in situ from suitable precursors. These include, for example, the lipases originally obtained from Humicola lanuginosa ( Thermomyces lanuginosus ), or further developed lipases, in particular those with the amino acid substitution D96L.

It is also possible to use enzymes which are summarized under the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases.

To increase the bleaching effect, oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention. Advantageously, preferably organic, particularly preferably aromatic, compounds interacting with the enzymes are added in order to increase the activity of the oxidoreductases concerned (enhancers) or to ensure the flow of electrons (mediators) in the event of greatly differing redox potentials between the oxidizing enzymes and the soiling.

A protein and / or enzyme can be protected against damage such as inactivation, denaturation or disintegration, for example due to physical influences, oxidation or proteolytic cleavage, particularly during storage. In the case of microbial production of the proteins and / or enzymes, inhibition of proteolysis is particularly preferred, in particular if the agents also contain proteases. Washing or cleaning agents can contain stabilizers for this purpose; the provision of such means represents a preferred embodiment of the present invention.

Proteases and amylases that are active in washing or cleaning are generally not provided in the form of the pure protein, but rather in the form of stabilized, storable and transportable preparations. These ready-made preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, in particular in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, with little water and / or with stabilizers or other auxiliaries.

Alternatively, the enzymes can be encapsulated both for the solid and for the liquid dosage form, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are enclosed as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a protective layer impermeable to water, air and / or chemicals. Additional active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes, can also be applied in superimposed layers. Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Such granules are advantageously low in dust, for example due to the application of polymeric film formers, and due to the coating are stable in storage.

Furthermore, it is possible to pack two or more enzymes together so that a single granulate has several enzyme activities.

As can be seen from the previous statements, the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations. Protease and amylase preparations preferably used according to the invention contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, particularly preferably between 0.4 and 20% by weight and in particular between 0, 8 and 10% by weight of the enzyme protein.

Automatic dishwashing agents which, based in each case on their total weight, contain 0.1 to 12% by weight, preferably 0.2 to 10% by weight and in particular 0.5 to 8% by weight of enzyme preparations are particularly preferred .

In addition to the aforementioned nonionic surfactants to be used according to the invention, the automatic dishwashing agents according to the invention can also contain further nonionic surfactants.

The proportion by weight of the further nonionic surfactant in the total weight of the automatic dishwashing agent according to the invention is in a preferred embodiment between 0.1 and 30% by weight, preferably between 0.5 and 20% by weight, preferably between 1 and 10% by weight in particular between 2 and 6% by weight.

In a preferred embodiment, preferred further nonionic surfactants have the general formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (CH ₃ ) O] _z CH ₂ CH (OH ) R ² , in which R ^{1 stands} for a linear or branched aliphatic hydrocarbon radical with 4 to 22 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x and z for values between 0 and 40 and y is a value of at least 15.

The addition of these nonionic surfactants has proven to be particularly advantageous with regard to the rinsing performance and drying. In a preferred embodiment, the automatic dishwashing agent contains, based on its total weight, nonionic surfactant of the general formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH _2O ] _y [CH ₂ CH (CH ₃ ) O] _z CH ₂ CH (OH) R ² in amounts of 0.1 to 15% by weight, preferably 0.2 to 10% by weight, particularly preferably 0.5 to 8% by weight and in particular 1.0 up to 6% by weight.

Particularly preferred are those end-capped poly (oxyalkylated) nonionic surfactants which, according to the formula R ¹ O [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ² , in which R ¹ denotes a linear or branched aliphatic hydrocarbon radical with 4 up to 22 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and y stands for a value between 15 and 120, preferably 20 to 100, in particular 20 to 80. The group of these nonionic surfactants includes, for example, hydroxy _mixed ethers of the general formula C _6-22 -CH (OH) CH ₂ O- (EO) _20-120 -C _2-26 , for example the C _8-12 fatty alcohol (EO) ₂₂ - 2-hydroxydecyl ethers and the C _4-22 fatty alcohol (EO) _40-80 -2-hydroxyalkyl ethers.

Automatic dishwashing detergent according to the invention, characterized in that a surfactant of the general formula R ¹ CH (OH) CH ₂ O- (CH ₂ CH ₂ O) _20-120 - R ^{2 is} used as a further nonionic surfactant, R ¹ and R ^{2 being} independent each other for a linear or branched aliphatic hydrocarbon radical having 2 to 20 carbon atoms are particularly preferred.

Also preferred are surfactants of the formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH _2O ] _y CH ₂ CH (OH) R ² , in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical with 4 to 22 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x denotes values between 0.5 and 4, preferably 0.5 to 1.5, and y denotes a value of at least 15 stands.

According to the invention, surfactants of the general formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH _2O ] _y CH ₂ CH (OH) R ^{2 are also} preferred, in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical with 4 to 22 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x stands for a value between 1 and 40 and y stands for a value between 15 and 40, the alkylene units [ CH ₂ CH (CH ₃ ) O] and [CH ₂ CH ₂ O] are randomized, ie in the form of a statistical, random distribution.

The group of preferred end-capped poly (oxyalkylated) nonionic surfactants also includes nonionic surfactants of the formula R ¹ O [CH ₂ CH ₂ O] _x [CH ₂ CH (R ³ ) O] _y CH ₂ CH (OH) R ² , in which R ¹ and R ² independently of one another represents a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical with 2 to 26 carbon atoms, R ^{3 is} independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ - CH ₃ , —CH (CH ₃ ) ₂ , but preferably —CH ₃ , and x and y independently of one another have values between 1 and 32, nonionic surfactants with R ³ = —CH ₃ and values for x from 15 to 32 and y of 0.5 and 1.5 are particularly preferred.

By using the nonionic surfactants described above with a free hydroxyl group on one of the two terminal alkyl radicals, the rinsing performance and drying can be significantly improved compared to conventional polyalkoxylated fatty alcohols without a free hydroxyl group.

The specified carbon chain lengths and degrees of ethoxylation or degrees of alkoxylation of the aforementioned nonionic surfactants represent statistical mean values which, for a specific product, can be an integer or a fraction. Due to the manufacturing process, commercial products of the formulas mentioned mostly do not consist of an individual representative, but rather of mixtures, which can result in mean values and fractional numbers for both the carbon chain lengths and the degrees of ethoxylation or alkoxylation.

Of course, the aforementioned nonionic surfactants can be used not only as individual substances but also as surfactant mixtures of two, three, four or more surfactants. Surfactant mixtures are not mixtures of nonionic surfactants which in their entirety fall under one of the above general formulas, but rather those mixtures which contain two, three, four or more nonionic surfactants which are described by different ones of the above or other general formulas can be.

Those nonionic surfactants which have a melting point above room temperature are particularly preferred. Nonionic surfactant (s) with a melting point above 20 ° C., preferably above 25 ° C., particularly preferably between 25 and 60 ° C. and in particular between 26.6 and 43.3 ° C., is / are particularly preferred .

1. a) 0,001 bis 0,5 Gew.-% des Mn-haltigen Bleichkatalysators Mn-TACN;
2. b) 0,1 bis 5 Gew.-% Polyvinylpyrrolidon-Partikel mit einem mittleren Teilchendurchmesser von 100 bis 150 µm, insbesondere von 110 bis 130 µm;
3. c) 2 bis 30 Gew.-% Bleichmittel, insbesondere Natriumpercarbonat;
4. d) gegebenenfalls 1 bis 15 Gew.-% eines copolymeren anionisches Polymers aus der Gruppe der Polycarboxylate und Polysulfonate

Particularly preferred automatic dishwashing detergents according to the invention contain

1. a) 0.001 to 0.5% by weight of the Mn-containing bleach catalyst Mn-TACN;
2. b) 0.1 to 5% by weight of polyvinylpyrrolidone particles with an average particle diameter of 100 to 150 μm, in particular 110 to 130 μm;
3. c) 2 to 30% by weight of bleach, especially sodium percarbonate;
4. d) optionally 1 to 15% by weight of a copolymeric anionic polymer from the group of polycarboxylates and polysulfonates

1. a) 0,001 bis 0,5 Gew.-% des Mn-haltigen Bleichkatalysators Mn-TACN;
2. b) 0,1 bis 5 Gew.-% Polyvinylpyrrolidon-Partikel mit einem mittleren Teilchendurchmesser von 100 bis 150 µm, insbesondere von 110 bis 130 µm;
3. c) 2 bis 30 Gew.-% Bleichmittel, insbesondere Natriumpercarbonat;
4. d) gegebenenfalls 1 bis 15 Gew.-% eines copolymeren anionisches Polymers aus der Gruppe der hydrophob modifizierten Polycarboxylate und Polysulfonate.

Further particularly preferred automatic dishwashing agents according to the invention contain

1. a) 0.001 to 0.5% by weight of the Mn-containing bleach catalyst Mn-TACN;
2. b) 0.1 to 5% by weight of polyvinylpyrrolidone particles with an average particle diameter of 100 to 150 μm, in particular 110 to 130 μm;
3. c) 2 to 30% by weight of bleach, especially sodium percarbonate;
4. d) optionally 1 to 15% by weight of a copolymeric anionic polymer from the group of the hydrophobically modified polycarboxylates and polysulfonates.

In addition to the ingredients described above, the agents according to the invention can contain other washing or cleaning-active substances, preferably from the group of bleaches, bleach activators and bleach catalysts, glass corrosion inhibitors, corrosion inhibitors, fragrances and perfume carriers. These preferred ingredients are described in more detail below.

1. a) ein erfindungsgemäßes maschinelles Geschirrspülmittel;
2. b) eine Anleitung, die den Verbraucher darauf hinweist, das maschinelle Geschirrspülmittel ohne Zusatz eines Klarspülers und/oder eines Enthärtersalzes zu verwenden ist, ist ein weiterer Gegenstand dieser Anmeldung.

The active ingredient combinations described above are particularly suitable for cleaning dishes in automatic dishwashing processes. Another object of the present application is a method for cleaning dishes in a dishwasher using an automatic dishwashing agent according to the invention, the automatic dishwashing agent preferably being metered into the interior of a dishwasher while a dishwasher program is running, before the start of the main wash cycle or during the main wash cycle will. The metering or introduction of the agent according to the invention into the interior of the dishwasher can take place manually, but the agent is preferably metered into the interior of the dishwasher by means of the metering chamber of the dishwasher. In the course of the cleaning process, no additional water softener and no additional rinse aid are preferably dosed into the interior of the dishwasher. A kit for a dishwasher, comprising

1. a) an inventive automatic dishwashing agent;
2. b) Instructions that advise the consumer to use the automatic dishwashing detergent without the addition of a rinse aid and / or a softening salt are another subject of this application.

The automatic dishwashing detergents according to the invention show their advantageous cleaning and drying properties, especially in low-temperature cleaning processes. Preferred dishwashing processes using agents according to the invention are therefore characterized in that the dishwashing processes are carried out at a liquor temperature below 60.degree. C., preferably below 50.degree.

As described at the outset, agents according to the invention are distinguished from conventional automatic dishwashing agents by an improved drying performance. The present application therefore also relates to the use of an automatic dishwashing agent according to the invention for improving drying in automatic dishwashing.

Some exemplary recipes for preferred automatic dishwasher tablets can be found in the following tables (recipes 13 to 16, 25 to 28 and 37 to 40 are preferred recipes according to the invention):

Embodiments

Approx. 1% by weight of cross-linked PVP particles were incorporated into a commercially available detergent tablet for machine dishwashing, which contains a bleach catalyst as an effective bleach-boosting ingredient. The cleaning performance of the tablet was then checked in a machine cleaning process on bleachable soiling (tea). In comparison, the cleaning performance of the cleaning tablet was tested without cross-linked PVP particles. This was followed by a visual assessment of the cleaning performance on a scale from 1 to 10 (1 is the worst, 10 the best).

The cleaning results at 40 ° C are shown below: Table 1: Cleaning results on tea Tablet with bleach catalyst without PVP 4.3 Tablet with bleach catalyst and PVP 6.5

The results shown make it clear that the cleaning performance on bleachable soiling could be significantly increased by adding PVP particles.

Claims (10)

1. An automatic dishwashing detergent in the form of a pressed shaped body, containing polyvinylpyrrolidone particles and at least one bleach catalyst, a manganese complex having the macromolecular ligands 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), 1,4,7-triazacyclononane (TACN) and/or 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane (Me/Me-TACN), selected from [Mn^III ₂(µ-O)₁(µ-OAc)₂(TACN)₂](ClO₄)₂, [Mn^IIIMn^IV(µ-O)₂(µ-OAc)₁(TACN)₂](BPh₄)₂, [Mn^IV ₄(µ-O)₆(TACN)₄](ClO₄)₄, [Mn^III ₂(µ-O)₁(µ-OAc)₂(Me-TACN)₂](ClO₄)₂, [Mn^IIIMn^IV(µ-O)₁(µ-OAc)₂(Me-TACN)₂](ClO₄)₃, [Mn^IV ₂(µ-O)₃(Me-TACN)₂](PF₆)₂ and [Mn^IV ₂(µ-O)₃(Me/Me-TACN)₂](PF₆)₂, being used as the bleach catalyst, the polyvinylpyrrolidone particles having an average particle diameter of from 100 to 150 µm.
2. The automatic dishwashing detergent according to claim 1, characterized in that it is in the form of a compacted body, in particular in the form of a tablet.
3. The automatic dishwashing detergent according to one of claims 1 to 2, characterized in that the polyvinylpyrrolidone particles are contained in an amount of from 0.1 to 5 wt.%, in particular in an amount of from 0.2 to 3 wt.%, especially in an amount of from 0.3 to 1.8 wt.%.
4. The automatic dishwashing detergent according to one of claims 1 to 3, characterized in that it contains at least one bleaching agent.
5. The automatic dishwashing detergent according to one of claims 1 to 4, characterized in that it contains at least one bleach activator.
6. The automatic dishwashing detergent according to one of claims 1 to 5, characterized in that it contains at least one anionic polymer, preferably selected from copolymeric polycarboxylates and copolymeric polysulfonates.
7. The automatic dishwashing detergent according to one of the preceding claims, characterized in that it additionally contains at least one builder and at least one enzyme.
8. The automatic dishwashing detergent according to claim 7, characterized in that the builder is selected from salts of tripolyphosphate, carbonic acid and citric acid and mixtures thereof.
9. An automatic dishwashing method, characterized in that an automatic dishwashing detergent according to one of the preceding claims is used.
10. The use of a dishwashing detergent according to one of claims 1 to 8 for removing bleachable stains, in particular tea stains.